Lawrence Berkeley National Laboratory

In-cavity complexes and their bonding features between thio-crown (TC) ethers and f-elements are unexplored so far. In this paper, actinyl(VI) (An = U, Np, Pu, Am, and Cm) complexes of TC ethers have been characterized using relativistic density functional theory. The TC ether ligands include tetrathio-12-crown-4 (12TC4), pentathio-15-crown-5 (15TC5), and hexathio-18-crown-6 (18TC6). On the basis of the calculations, it is found that the "double-decker" sandwich structure of AnO₂(12TC4)₂²⁺ and "side-on" structure AnO₂(12TC4)²⁺ are changed to "insertion" structures for AnO₂(15TC5)²⁺ and AnO₂(18TC6)²⁺ due to increased size of the TC ether ligands. The actinyl monocyclic TC ether complexes are found to exhibit conventional conformations, with typical An-O_actinyl and An-S_ligand distances and angles. Chemical bonding analyses by Weinhold's natural population analysis (NPA), natural localized molecular orbital (NLMO), and energy decomposed analysis (EDA), show that a typical ionic An-S_ligand bond with the extent of covalent interaction between the An and S atoms primarily attributable to the degree of radial distribution of the S 3p atomic orbitals. The similarity and difference of the oxo-crown and TC ethers as ligands for actinide coordination chemistry are discussed. As soft S-donor ligands, TC ethers may be candidate ligands for actinide recognition and extraction.